CN104084188A - Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst - Google Patents

Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst Download PDF

Info

Publication number
CN104084188A
CN104084188A CN201410300238.6A CN201410300238A CN104084188A CN 104084188 A CN104084188 A CN 104084188A CN 201410300238 A CN201410300238 A CN 201410300238A CN 104084188 A CN104084188 A CN 104084188A
Authority
CN
China
Prior art keywords
catalyst
photo
temperature
bivo
invo
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410300238.6A
Other languages
Chinese (zh)
Inventor
戴洪兴
吉科猛
邓积光
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing University of Technology
Original Assignee
Beijing University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing University of Technology filed Critical Beijing University of Technology
Priority to CN201410300238.6A priority Critical patent/CN104084188A/en
Publication of CN104084188A publication Critical patent/CN104084188A/en
Pending legal-status Critical Current

Links

Abstract

The invention discloses a visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and an application of the photo-catalyst, belonging to the technical field of photo-response catalysts. A preparation method of the photo-catalyst comprises the following steps: dissolving indium nitrate, bismuth nitrate and ascorbic acid in a mixed solvent consisting of ethylene glycol, methyl alcohol, concentrated hydrochloric acid and deionized water according to a mole ratio of 4 to 1 to 5, then transferring to a water bath kettle at the temperature of 70 DEG C for further stirring, adding ammonium metavanadate with molar weight equal to that of total nitrate, dipping a PMMA (Polymethyl Methacrylate) template in a precursor solution; carrying out suction filtration and drying, then obtaining a target catalyst through a two-step roasting method. The two-step roasting method comprises the following steps: (1) increasing the temperature from the room temperature to 300 DEG C at the rate of 1 DEG C per minute and maintaining for 3 hours in the nitrogen atmosphere; (2) switching to the air atmosphere when the temperature is reduced below 50 DEG C, and increasing the temperature to 450 DEG C at the rate of 1 DEG C per minute and maintaining for 4 hours. The photo-catalyst has efficient photo-catalytic activity on the degradation of rhodamine B and methylene blue under the irradiation of visible light.

Description

A kind of three-dimensional ordered macroporous InVO 4-BiVO 4the visible light responsive photocatalyst of hetero-junctions, preparation and application
Technical field
The present invention relates to a kind of visible light-responded three-dimensional ordered macroporous material that has, relate in particular to catalysis material, preparation and the application of the organic dyestuff such as efficient degradation rhodamine B and methylene blue under radiation of visible light, belong to visible light response catalyst technical field.
Background technology
Monoclinic phase InVO 4there is good visible light catalysis activity, in photochemical catalyzing and degradation of sewage, there is tempting application prospect the aspect such as organic matter, and its traditional preparation method comprises solid phase method (J.Ye, et.al., J.Chem.Phys.Lett.2002,356:221), hydro-thermal method (G.C.Xiao, et.al., Chinese J.Inorg.Chem.2004,20:195), sol-gel process (L.Zhang, et.al., J.Solid State Chem.2006,179:804) etc.This seminar piles up with polymethyl methacrylate (PMMA) microballoon the hard template with ordered 3 D structure forming recently and has prepared the monoclinic phase InVO with three-dimensional ordered macroporous (3DOM) structure 4(Y.Wang, et.al., Chem.Eng.J.2013,226:87), its degradation of methylene blue (MB) dye sheet under radiation of visible light has revealed higher visible light catalysis activity, but degrading activity poor (Y.Wang, et.al. to rhodamine B (RhB) dyestuff, Solid State Sci.2013,24:62).Monoclinic phase BiVO 4that another kind has the new material compared with high visible light catalytic activity.This seminar once adopted hydro-thermal method to synthesize to have porous American football shape, multi-branched shape, porous eight angle type, leaf shape, bar-shaped, bouquet shape, tubulose etc. the monoclinic phase BiVO of different morphologies 4, they are separated the organic dyestuff such as methyl orange and MB in radiation of visible light decline and show equally good photocatalysis performance (X.Meng, et.al., Mater.Chem.Phys.2011,125:59), but photocatalysis performance is still not ideal enough.This seminar also once developed the 3DOM BiVO for degradation of phenol 4photochemical catalyst, its photocatalytic activity is compared with American football shape BiVO 4increase.Research finds, the factor that affect photocatalytic activity is a lot, for the method for modifying of these influence factors mainly round improve material to the absorption of luminous energy with conversion and promote the effective separated of photo-generated carrier and catch.Up to now, researcher sums up the photocatalytic activity that following methods improves material: (a) material of preparation table mask defectiveness structure; (b) reduce particle size; (c) make composite semiconductor; (d) doped metal ion.
Up to now, there is no document and patent report and cross the InVO that this kind has hetero-junctions and 3DOM structure 4-BiVO 4composite photocatalyst.
Summary of the invention
The object of the present invention is to provide a kind of three-dimensional ordered macroporous InVO of preparation 4-BiVO 4visible light responsive photocatalyst of hetero-junctions and preparation method thereof, this catalyst has the 3DOM structure of hetero-junctions and periodic distribution, specific area is large, porosity is high and hole wall on be distributed with meso-hole structure, the organic dyestuff such as RhB, MB of can degrading efficiently.The PMMA hard template method that to be specifically related to take ascorbic acid be complexing agent.
A kind of three-dimensional ordered macroporous InVO 4-BiVO 4the visible light responsive photocatalyst of hetero-junctions, is characterized in that, this catalyst be have on three-dimensional ordered macroporous structure and hole wall, have meso-hole structure by monoclinic phase InVO 4and BiVO 4the photochemical catalyst of forming composite structure, average pore size is 100～200nm, and hole wall wall thickness is 20～40nm, and the mesoporous aperture of hole wall is 2～10nm, and band-gap energy is 2.5～2.6eV.Above-mentioned 3DOM InVO 4-BiVO 4the preparation method of visible light responsive photocatalyst, it is characterized in that, adopt PMMA microsphere template legal system standby, key step comprises: under stirring condition, 4:1:5 is dissolved in indium nitrate, bismuth nitrate and ascorbic acid in the mixed solvent of ethylene glycol, methyl alcohol, concentrated hydrochloric acid and deionized water formation in molar ratio, then the solution obtaining is shifted as for continuing in the water-bath of 70 ℃ and stirred, ammonium metavanadate with total nitrate equimolar amounts is joined to above-mentioned solution, after dissolving completely, the temperature of this solution is down to room temperature.Wherein, the corresponding 1.5mL ethylene glycol of every 10mmol ascorbic acid, 7.5mL methyl alcohol, 1.0mL mass fraction are 68wt% concentrated hydrochloric acid and 7.0mL deionized water; The poly (methyl methacrylate) micro-sphere that takes ordered arrangement forms hard template and in precursor liquid, floods 3h, after suction filtration, under room temperature, is dried; The predecessor of gained is placed in to tube furnace and by two one-step baking methods, obtains target light catalyst: (1) at nitrogen atmosphere, with the speed of 1 ℃/min, from room temperature, rise to 300 ℃ and keep 3h under this temperature; (2) treat that tube furnace temperature is down to below 50 ℃, switch to air atmosphere, with the speed of 1 ℃/min, rise to 450 ℃ and keep 4h at this temperature; Be cooled to room temperature, obtain three-dimensional ordered macroporous InVO 4-BiVO 4the visible light responsive photocatalyst of heterojunction structure.
Three-dimensional ordered macroporous InVO of the present invention 4-BiVO 4the visible light responsive photocatalyst of the hetero-junctions organic dyestuff such as sieve RhB and MB that can be used for degrading, under radiation of visible light, the degraded of RhB (initial concentration is 15mg/L) and MB (initial concentration is 20mg/L) is shown to efficient photocatalytic activity, the former can be degradable after radiation of visible light 70min, the latter's degradation rate after radiation of visible light 90min surpasses 85%, in photocatalysis depollution of environment field, has good application prospect.
Utilize the Instrument measuring gained target product 3DOM InVO such as D8ADVANCE type X-ray diffractometer (XRD), ZEISS SUPRA55 type SEM (SEM-EDS), JEOL-2010 type high-resolution electronic transmission microscopy (TEM) and SHIMADAZU-UV-2450 type ultraviolet-visual spectrometer (UV-Vis) 4-BiVO 4the crystal structure of photochemical catalyst, particle morphology, pore structure and extinction property.Utilize photo catalysis reactor to measure the degrade catalytic effect of RhB and MB of this catalyst under radiation of visible light.Result shows, according to the prepared 3DOM InVO of the inventive method 4-BiVO 4photochemical catalyst is mainly by monoclinic phase InVO 4with monoclinic phase BiVO 4mix and form, there is good three-dimensional ordered macroporous structure, the dye molecules such as RhB or MB of can degrading efficiently under radiation of visible light.
The method of testing of catalytic effect is as follows: the 100mL RhB solution that configuration concentration is 15mg/L (being 20mg/L for MB) is in photocatalysis quartz reactor, and adding 0.6mL mass fraction is the H of 30wt% 2o 2solution and add 0.1g InVO 4-BiVO 4the ultrasonic 30min of catalyst lucifuge, bubbling stirs, and stirs 3h after adding condensing unit in dark place again.Afterwards, this suspension is placed under visible ray and is irradiated and constantly stirring, from solution, get at regular intervals 5mL sample, the absorbance (at λ=665nm place) of test gained sample is to analyze the concentration of residual RhB (for MB, λ=554nm) wherein.
Accompanying drawing explanation
For further explanation the present invention, with embodiment and comparative example, elaborate below.Wherein:
Fig. 1 is prepared InVO 4-BiVO 4the XRD spectra of sample, wherein curve (a), (b) are respectively the XRD spectra of embodiment 1, comparative example 1 gained sample;
Fig. 2 is the prepared InVO of embodiment 4-BiVO 4the SEM of sample and TEM photo, wherein figure (a), (b) they are SEM photo and the EDS spectrogram of embodiment 1 gained sample, scheme (c), (d), (e), (f), be the TEM photo of embodiment 1 gained sample;
Fig. 3 is the prepared InVO of comparative example 1 4-BiVO 4the SEM photo of sample;
Fig. 4 is prepared InVO 4-BiVO 4the UV-Vis DRS spectrogram of sample and band-gap energy figure, wherein curve (a) and (b) correspond respectively to embodiment and comparative example;
Fig. 5 is prepared InVO 4-BiVO 4degrade under radiation of visible light efficiency (the initial concentration C of RhB of sample 0for 15mg/L) and degraded MB efficiency (initial concentration C 0for 20mg/L), wherein (a), (b), (c), (d) distinguish corresponding embodiment 1, embodiment 2, comparative example 1 and comparative example 2.
The specific embodiment
Below in conjunction with embodiment, the present invention will be further described, but the present invention is not limited to following examples.
Embodiment 1: under stirring condition, in the mixed solvent that the concentrated hydrochloric acid that successively 8mmol indium nitrate, 2mmol bismuth nitrate and 10mmol ascorbic acid to be dissolved in by 1.5mL ethylene glycol, 7.5mL methyl alcohol, 1.0mL mass fraction be 68wt% and 7.0mL deionized water form, then by obtaining solution, shift as for continuing stirring in the water-bath of 70 ℃, take again 10mmol ammonium metavanadate and join above-mentioned solution, to be dissolvedly the temperature of this solution is down to room temperature and adds 3g PMMA hard template, dipping 3h after completely.After suction filtration and drying at room temperature, gained predecessor is placed in to tube furnace and by two one-step baking methods, obtains target catalyst, two one-step baking methods are: (1) is (100mL/min) in nitrogen atmosphere, with the speed of 1 ℃/min, from room temperature, rise to 300 ℃ and keep 3h under this temperature; (2) treat that tube furnace temperature is down to below 50 ℃, switch to air atmosphere (100mL/min), with the speed of 1 ℃/min, rise to 450 ℃ and keep 4h at this temperature, then be down to room temperature, obtain 3DOM structure In VO 4-BiVO 4photochemical catalyst.Its phase composition is mainly monoclinic phase InVO 4and BiVO 4, aperture is 100～200nm, and hole wall wall thickness is 20～40nm, and the mesoporous aperture of hole wall is 2～10nm, and band-gap energy is 2.56eV.The RhB solution that configuration 100mL concentration is 15mg/L is in photocatalysis quartz reactor, and adding 0.6mL mass fraction is the H of 30wt% 2o 2solution and add 0.1g3DOM InVO 4-BiVO 4the ultrasonic 30min of catalyst lucifuge, bubbling stirs, and stirs 3h after adding condensing unit in dark place again.Afterwards, this suspension is placed under visible ray and is irradiated and constantly stirring, get 5mL sample every 10min from solution, get altogether 8 samples, test gained sample liquid is in the absorbance at λ=665nm place.After radiation of visible light 70min, RhB can be degradable.
Embodiment 2: the MB solution that configuration 100mL concentration is 20mg/L is in photocatalysis quartz reactor, and adding 0.6mL mass fraction is the H of 30wt% 2o 2solution and add 0.1gInVO prepared in embodiment 1 4-BiVO 4the ultrasonic 30min of catalyst lucifuge, bubbling stirs, and stirs 3h after adding condensing unit in dark place again.Afterwards, this suspension is placed under visible ray and is irradiated and constantly stirring, get 5mL sample every 10min from solution, get altogether 10 samples, test gained sample liquid is in the absorbance at λ=554nm place.After radiation of visible light 90min, the degradation efficiency of MB surpasses 85%.
Comparative example 1: under stirring condition, successively by 8mmol indium nitrate, 2mmol bismuth nitrate and 10mmol ascorbic acid are dissolved in the ethylene glycol by 1.5mL, 7.5mL methyl alcohol, 1.0mL mass fraction is in the concentrated hydrochloric acid of 68wt% and the mixed solvent of 7.0mL deionized water formation, then the solution obtaining is shifted as for continuing in the water-bath of 70 ℃ and stirred, take again 10mmol ammonium metavanadate and join above-mentioned solution, to be dissolved completely after, continue to add 1.972g P123 surfactant and 4mmol glucose, then this precursor liquid be diluted to 80mL (pH ≈ 2) and be transferred in 100mL teflon-lined stainless steel cauldron, it is placed in to the baking oven hydrothermal treatment consists 6h of 180 ℃, again products therefrom is filtered, washing, dry, grind, finally be placed in Muffle furnace, with the heating rate of 10 ℃/min, from room temperature, rise to 500 ℃ and at this roasting temperature 3h, be cooled to room temperature, obtain comparative sample InVO 4-BiVO 4catalyst.This sample is by a small amount of cube of blocky particle and a large amount of consisting of the coalescent porous spherical particle forming of nano particle, and main phase consists of quadrature phase InVO 4with monoclinic phase BiVO 4, band-gap energy is 2.53eV.The RhB solution that configuration 100mL concentration is 15mg/L is in photocatalysis quartz reactor, and adding 0.6mL mass fraction is the H of 30wt% 2o 2solution and add this InVO of 0.1g 4-BiVO 4the ultrasonic 30min of catalyst lucifuge, bubbling stirs, and stirs 3h after adding condensing unit in dark place again.Afterwards, this suspension is placed under visible ray and is irradiated and constantly stirring, get at regular intervals 5mL sample from solution, get altogether 12 samples, test gained sample liquid is in the absorbance at λ=665nm place.After radiation of visible light 180min, RhB degradation rate is 91%.
Comparative example 2: the MB solution that configuration 100mL concentration is 20mg/L is in photocatalysis quartz reactor, and adding 0.6mL mass fraction is the H of 30wt% 2o 2solution and add 0.1gInVO prepared in comparative example 1 4-BiVO 4the ultrasonic 30min of catalyst lucifuge, bubbling stirs, and stirs 3h after adding condensing unit in dark place again.Afterwards, this suspension is placed under visible ray and is irradiated and constantly stirring, get at regular intervals 5mL sample from solution, get altogether 13 samples, test gained sample liquid is in the absorbance at λ=554nm place.After radiation of visible light 180min, the degradation efficiency of MB is 80%.

Claims (3)

1. a three-dimensional ordered macroporous InVO 4-BiVO 4the visible-light-responsive photocatalyst of hetero-junctions, is characterized in that, this catalyst be have on three-dimensional ordered macroporous structure and hole wall, have meso-hole structure by monocline InVO 4and BiVO 4the photochemical catalyst of forming composite structure, average pore size is 100～200nm, and hole wall wall thickness is 20～40nm, and the mesoporous aperture of hole wall is 2～10nm, and band-gap energy is 2.5～2.6eV.
2. prepare three-dimensional ordered macroporous InVO claimed in claim 1 4-BiVO 4the method of the visible light responsive photocatalyst of hetero-junctions, is characterized in that, adopts poly (methyl methacrylate) micro-sphere template synthesis, specifically comprises the following steps:
(1) under stirring condition, 4:1:5 is dissolved in indium nitrate, bismuth nitrate and ascorbic acid in the mixed solvent of ethylene glycol, methyl alcohol, concentrated hydrochloric acid and deionized water formation in molar ratio, then the solution obtaining is shifted as for continuing in the water-bath of 70 ℃ and stirred, ammonium metavanadate with total nitrate equimolar amounts is joined to above-mentioned solution, after dissolving completely, the temperature of this solution is down to room temperature; Wherein, the corresponding 1.5mL ethylene glycol of every 10mmol ascorbic acid, 7.5mL methyl alcohol, 1.0mL mass fraction are 68wt% concentrated hydrochloric acid and 7.0mL deionized water;
(2) poly (methyl methacrylate) micro-sphere that takes ordered arrangement forms hard template and floods in precursor liquid, after suction filtration, under room temperature, is dried;
(3) predecessor of gained is placed in to tube furnace and obtains target light catalyst by two one-step baking methods: (1) at nitrogen atmosphere, with the speed of 1 ℃/min, from room temperature, rise to 300 ℃ and keep 3h under this temperature; (2) treat that tube furnace temperature is down to below 50 ℃, switch to air atmosphere, with the speed of 1 ℃/min, rise to 450 ℃ and keep 4h at this temperature, obtain three-dimensional ordered macroporous InVO 4-BiVO 4the visible light responsive photocatalyst of hetero-junctions.
3. a kind of three-dimensional ordered macroporous InVO described in claim 1 4-BiVO 4the visible light responsive photocatalyst of heterojunction structure is for rhodamine B degradation or methylene blue dye molecules.
CN201410300238.6A 2014-06-26 2014-06-26 Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst Pending CN104084188A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410300238.6A CN104084188A (en) 2014-06-26 2014-06-26 Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410300238.6A CN104084188A (en) 2014-06-26 2014-06-26 Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst

Publications (1)

Publication Number Publication Date
CN104084188A true CN104084188A (en) 2014-10-08

Family

ID=51632005

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410300238.6A Pending CN104084188A (en) 2014-06-26 2014-06-26 Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst

Country Status (1)

Country Link
CN (1) CN104084188A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017100057A (en) * 2015-11-30 2017-06-08 国立研究開発法人産業技術総合研究所 Semiconductor photocatalyst having characteristic absorption band and manufacturing method therefor
CN107973339A (en) * 2017-11-24 2018-05-01 武汉理工大学 The three-dimensional ordered macroporous calcium titanate photonic crystal and its synthetic method that a kind of porous nano-sheet is constructed
CN108855202A (en) * 2018-06-05 2018-11-23 上海交通大学 For photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303906A (en) * 2011-08-04 2012-01-04 北京工业大学 Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4
CN102872853A (en) * 2012-09-26 2013-01-16 北京工业大学 Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102303906A (en) * 2011-08-04 2012-01-04 北京工业大学 Ascorbic-acid-aided colloidal crystal template method used for preparing three-dimensionally ordered macroporous BiVO4
CN102872853A (en) * 2012-09-26 2013-01-16 北京工业大学 Three-dimensional ordered macroporous InVO4 visible light-responsive photocatalyst, preparation and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ENGUO WANG等: ""The Preration of InxBi1-xVo4 Photocatalyst Particles and their Photocatalytic Activity"", 《ADVANCED MATERIALS RESEARCH》, vol. 726731, 16 August 2013 (2013-08-16), pages 491 - 494 *
宋灵君: ""低维钒酸盐异质结构纳米材料的制备及性能研究"", 《中国优秀硕士学位论文全文数据库 工程科技I辑》, no. 01, 15 January 2013 (2013-01-15), pages 020 - 210 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2017100057A (en) * 2015-11-30 2017-06-08 国立研究開発法人産業技術総合研究所 Semiconductor photocatalyst having characteristic absorption band and manufacturing method therefor
CN107973339A (en) * 2017-11-24 2018-05-01 武汉理工大学 The three-dimensional ordered macroporous calcium titanate photonic crystal and its synthetic method that a kind of porous nano-sheet is constructed
CN107973339B (en) * 2017-11-24 2020-04-21 武汉理工大学 Three-dimensional ordered macroporous calcium titanate photonic crystal constructed by porous nanosheets and synthetic method thereof
CN108855202A (en) * 2018-06-05 2018-11-23 上海交通大学 For photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof

Similar Documents

Publication Publication Date Title
CN106914263B (en) A kind of preparation method of composite visible light catalyst
CN102992282B (en) Mesoporous C3N4 photocatalytic material prepared by using molten salt method and application thereof in photocatalysis field
Zhang et al. Fly ash cenospheres supported visible-light-driven BiVO4 photocatalyst: synthesis, characterization and photocatalytic application
Huang et al. Hierarchical porous ZnWO4 microspheres synthesized by ultrasonic spray pyrolysis: characterization, mechanistic and photocatalytic NOx removal studies
US20170057821A1 (en) Graphitic carbon nitride material, and its synthetic method and applications
CN105148975B (en) A kind of application of doped meso-porous g C3N4 catalysis materials of potassium in degrading organic dye waste water
Chen et al. Salt-assisted synthesis of hollow Bi2WO6 microspheres with superior photocatalytic activity for NO removal
CN104525266B (en) Preparation method of metal-organic framework material photocatalyst and application
CN104128184A (en) Floating type CoFe2O4/TiO2/floating bead composite photocatalyst and preparation method thereof
CN103480353A (en) Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst
CN108579779A (en) A kind of three-dimensional composite material, preparation method and the application in the removal of water pollutant visible light photocatalytic degradation
CN105664979A (en) Nano-mesoporous micro-spherical Ln-Bi5O7I photocatalyst and preparation method thereof
CN104525186A (en) Spherical bismuth molybdate nanocomposite having heterostructure as well as preparation method and application of nanocomposite
CN101791558A (en) Bismuth ferrite microsphere photocatalyst with hollow structure and preparation method thereof
CN104069848B (en) The hot legal system of a kind of alcohol is for the method for pure phase bismuth titanates and titanium oxide composite material
CN104353481A (en) Nitrogen-doped mesoporous carbon catalyst for wastewater degradation as well as preparation method and application thereof
CN107008473A (en) A kind of three-dimensional structure bismuth titanates nanometer sheet/perite nanometer piece composite photo-catalyst and preparation method thereof
CN104707542A (en) Photocatalyst/SiO2 composite aerogel material and preparation method thereof
Lu et al. Synthesis of visible-light driven CrxOy–TiO2 binary photocatalyst based on hierarchical macro–mesoporous silica
CN106694044B (en) A kind of preparation method of carbonitride/silver/Cu-BTC photochemical catalyst
CN103831093A (en) Zinc oxide based composite photocatalytic nano-material and preparation method thereof
CN104084215A (en) Three-dimensional ordered macroporous BiVO4-carrier Fe2O3 and precious metal photocatalyst (M/Fe2O3/3DOM BiVO4) and preparation method of photocatalyst
CN113072673A (en) Heating reflux preparation method and application of covalent organic framework material
CN105056938A (en) Method for improving photocatalytic activity of tungsten trioxide film
CN104084188A (en) Visible-light response photo-catalyst with three-dimensional orderly macropore InVO4-BiVO4 heterojunction, as well as preparation and application of photo-catalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20141008